Disazo dyestuffs



Patented Dec. 9, 1941 UNITED STATES PATENT OFFICE DISAZO DYESTUFFS Erich Fischer, Bad Soden in Taunus, and Richard Huss, Frankfort-on-the-Main, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October 15, 1940, Serial No. 361,252. In Germany October 24, 1938 6 Claims. (01.260-187) The present invention relates to disazo dye- 2,026,920 and 1,940,683, the new dyestuifs obstuffs; more particularly it relates to the dyetained with application of diazotized aminostuffs corresponding with the following general omega-sulfoacylaminobenzenes as initial comformula: ponents are distinguished by a better 'fastness to H038 NH-acyl I N n -N N HOKSX'C o N z E wherein the sulfoacylamino-group stands in Wet-processing and to perspiration.

metaor para-position to the azo-group, X The amines used as initial components in the stands for an alkyl group, Y for hydrogen or an process according to the present invention may alkyl group, Z for a methyl or acetylamino group, be prepared by condensing a nitroaminoor and wherein the benzene nuclei I and II may nitromonoalkylamino-benzene with a chloroacyl contain further substituents which do not lend chloride so as to form the corresponding nitrosolubility in water. (omega chloroacylamino) or nitro (omega We have found that valuable disazo dyestuffs chloroacyl N- alkylamino) benzene, then exare obtained by coupling a diazo compound of changing the chlorine atom for the sulfonic acid an amino-omega-sulfoacylamino-benzene of the group by means of sodium sulfite and subseformula: quently reducing the nitro-group.

NE: The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight, unless otherwise stated: (1) 23 parts of 1-amino-3-(omega-sulfoacetylamino)-benzene are dissolved in 100 parts by a volume of water and 45 parts by volume of 2N- Y caustic soda solution to form a clear solution, to wherein th sulfoacylamino-group Stands in which 6.9 parts of sodium nitrite are added. The metaor para-position to the amino-group X mixture iS then slowly introduced at 0 C.3 C. stands for an alkyl radical, Y for hydrogen or into an ly- 5 Solution of 25 Parts y V um o an alkyl radical, and wherein the benzene nucleus hydrochlorlc acld 0f 30 p cent- Strength. The

may t i further groups which do t 1 d solution of the diazo-compound thus obtained is solubility in water, with an amine of the benzene combined with the calculated amount of series which couples in para-position to the 3-methylbenzene in a feebly d medium- W n amino-group, with formation of a mono-azothe coupling is Complete, the -dYeStHfi dyestufl" further diazotizing t mono-azo dye is separated and further diazotized at 15 C. in

t fi and coupling t diazmcompound t a the usual manner in the presence of hydrochloric 2 m 5 h d n hth l 7 u1f ni acid in excess. The diazo-compound of the acid or a substitution product thereof as, for infl ufi is isolated, made into a Paste stance, a l-chloro-2r-acyIamino-B-hydroXynaphby means of water and coupled with Z-benzoylthalene-l-sulfonic acid. amino-5-hydroccynaphthalene-7-sulfonic acid in In this manner there are obtained dyestuffs a neutral to bicarbonate-alkaline medium. The which dye vegetables fibers bluish red to reddish disazo-dyestuff obtained is isolated in the usual blue tints. In comparison with similar disazo manner and dried. It dyes cotton in the dyestuffs, described in U. S. Patents Nos. Glaubers salt bath bluish red tints;

The dyestuff corresponds. with the following formula: V

(2) 23 parts of 1-amino-3-(omega-sulfoacetylamino) benzene are diazotized in the manner indicated in Example 1 and coupled with lamino-3-methylbenzene in a feebly acid medium. The diazo-com'pound of this monoazo dyestufi obtained as described in Example 1-, is coupled; While intensely stirring, at 0 C-.'3 0'. in a" neutral to bicarbonate-alkaline medium with a solution of the sodium salt of the mixed urea'from- 2-amino-5-hydroxynaphthalene 7-sulfonic acid and 1-amino-4-acety1aminobenzene. The dyestuff obtained dyes cotton clear, very bluish red' tints of very good fastness to wet-processing,

(3) 23 parts of l-aminol-(omega-sulfoacetylamino) -benzene are dissolved in 100' parts by volum e'of water and 50'parts by volume of asodium carbonate solution of 10 per cent strength. 6.9 parts of sodium nitrite are then added to the solution and the mixture is slowly introduced, while stirring, at 0 0., into hydrochloric acid in excess. The diazo-compound obtained which is partly precipitated, is then coupled with the calculated amount of 1-amino-3-methy1benzene.in a feebly acid medium. When the coupling is complete, the monoazo dyestuff is-separated and transformed in the usual manner into the diazo compound in the presence of hydrochloric acid in excess. The diazocompound obtained is then coupled, while intensely stirring, at 0 C., in a neutral to bicarbonate-alkaline medium with an aqueous solution of the sodium salt of the mixed urea from 2-amino-5-hydroxy-naphthalene-7- sulfonic acid and 1-amino-4-acetylaminobenzene. When the coupling is complete, the dyestufi is isolated and dried. It dyes cotton bluish Bordeaux tints of very good fastness to wet-process- (4') 23 parts of I-aminol-(omega-sulfoacetylaminol-behz'ene' are transformed into the diazo compound inthe manner indicated in Example 3". The dia'zoco-mpound obtained is coupled with the calculated amount of 1-amino-2.3-dimethylbenzene in a feebly acid medium. When the coupling is complete, the monoazo dyestuff is diazotizedat 15 C.,in;the usual manner withthe calculated amount'of; sodium nitrite in the presence of hydrochloric acid in excess. The diazoa compound obtained is then combined at O" C.-5 C. in a neutral to bicarbonate-alkaline medium with an aqueous solution of the sodium salt of 2-acetylaminoe5-hydroxynaphtha1ene'-7-sulfonic-acid. When the coupling is complete, the disazo-dyestuff is filtered with suction and dried. It dyes cotton Bordeaux tints of good fastness to wet-processing.

The following table indicates the" shades of a number of other disa'zo' dyestuffs obtainable by this invention which have similar properties of fastness:

Diazo component Middle component End component I Shade 1 l-amino-3- (omega sulfoacetylamino) 1-amino-3-n1ethyl-benzene .e 2- (benzoyl -amino -4 -benzoyl -amino) -5-j Blnish red.

benzene. V 11ydroxy-naphthalene-7-sulfonic acid. 2 1-amino-3-(omega-sulfoacetylamino) d0 5-hyd10xy-7sulfo-2-naphthyl-urea Do. '4-ch'lorobenzene. r v n 3 Lamina-'3 (omega-sulfoacetylamino) do .J Mixed urea from 2-a1n1no-5-hy'droxy- Do.

- fi-chlorobenzene. naphthalene-7-sulion1c acid and l-amino- I i I 1 4-acetyl-aminobenzene.

4 1-an1ino-3- (omega-sulfoacetylamino) .d0 ..d0 Do.

G-chlorobenzene. V 5 l-amino-3-(omega-sulfoacetyl-N-meth- -do Do.

I ylamino)-benzene. t 6 l amino 3 (omega sulfopropionyl- .do. 2- (benzoylannno -4 -benzoylam1no)-5-hy- Do.

amino) -benzene. a droxynaphthalene-7 sulfonic acid. 7 l-aminc-S- (omega-suli'oacetylamino) Lamina-2.3- li-methylbenzene. Mixed urea from 2rammo-5-hydroxy-naph- Bluish bordeaux.

. benzene. tha1ene-7-sulfonic acid and l-ainino-i- 1 acetylaminobenzene. V 8 1- amino 4 (omega sulfopropionyl l-amino-3 methyl-6-methoxy- 2-(benzoylamino i'-benzoylamino) -5-hy- Violetish' subdued aniino)-benzene. benzene. droxy-naphthalene-7-sulfonic acid. blue. 9 1-an1ino-4- (omega-sulfoacetylamino) do 2-(benzoylamlnoi-benzoylamino) '-5-hy- Subdued bluish benzene. droxynaphthalene-7-sulfonic acid. violet. 10 l-a'mino-ei-(oinega-sulfoaeetylarnino) 1-amino-3-mctl1yl-benzene. Mlxed urea irom 2amino-5-hydroxy- Ruby. fi-chlorob'enzene. Y naphthalene-7-sulfonic acidand l-amino- 4-acetylaminobenzene. g 11 l-amino-4-(omega sulfoacetylamino) 6 .do. l; do Bordeaux.

chlorobenzene. I Y 12 l-amino-2.6-di-chloro-4- (omega-sulfo- .d0 Mixed urea from?-amino-5-hydroxynaph- Bluish red.

' acetylamino)-benzene; 'thalene-7-sulfomc acid and l-amino-4- v v acetylaminobenzene. 13 l-amino-4.6-di-ch1or0-3-(Omega-sull'o- ...d0 .-do' Bordeaux. acetylamino)-benzene. 14 l-amino-B- (omega-sulfoacetylamino)- l-amino-3-methyl-benzene. .2 -benzoyl am1no 6 -hydroxynaphthalene Bluishred.

. i-methylbenzene. 7-su1fomc acid. 15 1:- amino 3 (omega sulfopropionyl do. d Do.

amino)-4.6-dimethy1-benzene. V V 16 1-amino-4 (oniega-sulioacetylaniino) i0 .'.-do Bordeaux.

5-methoxybenzene. I 17 1-amino-3-(omega-sulfoacetylamino)- .do. Mixed urea from 2-amino-5-hydroxy- Do.

6-chloro-4-methyl-benzene. naphthalcne-7-sulionic acid andl-ami-no- 4 y H 1 e-acetyl-aminobenzene v ,18 1-an1in0-4- (omega-sulfoacetylamino) 1 -ammo 3 acetyl -amn1obenz-benzoyla' o 5'- hydroxynaphthalene- D0. 2-chlorobenzene. zene. i 7-sulfonic acid V 19 l-aminoi-(omega-sulfoactatylamino): l-amino-il-acetyl-ammo-fido. Do.

benzene. methyl-benzene:

We claim: 1. The disazo dyestuffs corresponding with the following general formula:

good fastness properties, especially of very good fastness to wet-processing.

wherein the sulfoacylamino-group stands in one of the positions metaand parato the am- 3. The disazo dyestuffs corresponding with the following general formula:

H OaS-CHr-C O-HN C Ha OH group, X stands for a lower alkyl group, Y for a member of the group consisting of hydrogen and methyl, Z1 and Z2 stand for members of the group consisting of hydrogen, halogen, alkyl and alkoxy, a1 stands for a member of the group consisting of methyl and acetylamino, and 112 for a member of the group consisting of hydrogen, methyl and methoxy, being dark red to dark brown powders which dye vegetable fibers bluish-red to reddish- Ca V blue shades of good fastness properties, especially of very good fastness to wet-processing.

2. The disazo dyestuffs corresponding with the following general formula:

HOaS-CHz-C O-EN wherein the sulfoacylamino-group stands in one HOaSCHzCOHN CH:

of the positions metaand parato the azo-group,

X stands for a lower alkyl group, Y for a member of the group consisting of hydrogen and methyl, Z1 and Z2 stand for members of the group consist- HOaS being a red powder which dyes vegetable fibers clear buish-red shades of good fastness properties, especiall of very good fastness to wet-processing.

Zn HO3S- NH-acyl CH; H

5. The disazo dyestuff of the following formula:

being a red powder which dyes vegetable fibers clear bluish-red shades of good fastness properties, especially of very good fastness to wet-processing.

6. The disazo dyestuif of the following formula:

ing of hydrogen, halogen, alkyl and alkoxy, being dark red to dark brown powders which dye vegetable fibers bluish-red to reddish-blue shades of being a red powder which dyes vegetable fibers clear Bordeaux shades of good fastness properties, especially of very good f-astness to wet-processing.

ERICH FISCHER. RICHARD I-IUSS. 

